Process of continuous sulphonation of benzene, applicable to impure benzenes



' P. A. BARBET PROCESS OF CONTINUOUS SULPHONATION OF BENLENE, APPLICABLE {TO IMPURE BENZENES Filed April 25 1917 Patented Jane 19, 1923. x i I I UNITED STATES PATENT OFFICE.

PIERRE ALEXANDRE BARBET. OF PARIS, FRANCE.

PROCESS OF CONTINUOUS SULPHONATION OF BENZENE, APPLICABLE TO IMPURE BENZENES.

Application filed ltpril 23, '1917. serial No. 163,898.

Touni/11mm.Manny concern. {The apparatus has the general configura- Be it known that l, PIERRE ALEXANDRE tldn of a continuous distilling column. Banner. citizen of the French Republic, re- A indicates acolumn of plates provided siding at 5 line de lllchelle, Paris, France. with bubbling caps of any type. There are 5 have invented certain new and useful Iminterposed therein some special plates called provements in Processes of Continuous Sulheating plates. wherein. for instance heatin phonation of Benzene, Applicableto Impure coils are arranged on the said plates' thes e Benzenes. of which the following 15 a speclfilatter have for their object to maintain the cation. temperature of the acid liquid at the desired Benzene is easily attacked by heated Suldegree. When desired, the bubbling plates P1111!ic Mid and Still more eilslly y fuming may be further combined with heating coils sulphuric acid; and the combination or comextending between the rows of caps. 4 pound so formed (benzene sulphonic acid) The fuming sulphuric acid i i t d d may serve as a base for further transform& in a continuous manner at the top of the 15 tions. particularly for the synthetic produccolumn, preferably after the am i h t d ti f h ol, to the desired temperature by means of a Benzene is generally sulphonatcd by diS- heater D provided with a coil. continuous operations in large cast iron boil- Benzene. whether pure or mixed with ers or stills which are closed and provided gasoline. is also introduced in a continuous 20 i h a, i way and controlled by the cock or valve R.

The circumstances have led to use for such The same becomes heated within the heat ina reaction impure benzenes. specially those terchanger B by means of the heat contained whi h a e cX lflt ed fIOIII e 3011180 in the sulphonated products which flow out Malaysias gasolines. benzenes which hard y ot' the lower part of the column A.

contain 50-55% of benzene. the remaining The same then passes through the heaterbeing an oil which cannot be sulphonated. vaporizer C. wherein the benzene will be en- The presence of so important a quantity f tirely vaporized.

gasoline or petroleum hydrocarbons does not The benzene will enter at the bottom of A,

prevent sulphonation of the benzene. but the rise and pass through the whole of the plates same nevertheless constitutes a very great i cc i nuisance. on the one hand by the space it In the lower ones. the same will meet an usplvgsly occupies within the sulphonating acid which is already almost entirelv transapparatus. whereby its daily product'ivencss formed into benzene sulphonic acid and will will 1, lpssenetL and on the other hand by finally saturate the said acid. Then pro- 35 reason of the temperature which must be gressively. as far as the vapour becomes attained. whi h will cau e the d e pment poorer and poorer in benzene and consists of of high pressures due to the vaporization of a larger proportion of oil. the same ill the petroleum hydrocarbons. bubble into acid which is increasingly ca- The present invention is a process whereby pable of taking up benzene, and finally will the said bcnzenes may be sulphonated in a in the upper plate pass through fresh acid,

continuous way. of the maximum density and sulphonating The said process essentially consists in power.

bringing in a continuous manner the ben- Moreover, when it is considered that, by

Zeno, either pure or charged with oil or this system. the benzene vapour, at each unit other impurities. in the. state of vapor into of time, will only represent a relatively small an intimate. methodical and sufiiciently proquantity compared with the quantity of acid longed contact with fuming sulphuric acid, with which it is brought into association, it

heated and constantly maintained at the dewill be at once understood that the last porsired temperature, the said acid being introtions of benzene will be retained.

50 duced in a continuous way and the benzene The vapours of the unsulphonatable consulphonic acid so produced being abstracted stituent of the material treated will flow also in a continuous manner. through the acid and pass to the cooler E,

The details of this process will be pointed then to the test-glass F and thence to out in the following description, the continuous purifier H, which -is fed with water by the cook or valve L and serves to retain the acid carried away (particularly a small quantity of sulphurous acid) and finally the gasoline 'freed from benzene and in a pure state will flow into the tank K.

The benzene sulphonic acid, which was formed during the gradual descent of the acid from plate to plate, will flow out of the pipe I), give up its heat to the entering benzene and finally flow into a tank G, wherein it will be cooled by means of a water-coil.

Such, is the whole operation.

As for the details of construction of the apparatus employed, the same may be varied within a certain limit.

With regard to the materials to be used in constructing the apparatus, it may be stated that experience has proved'that cast iron is very little corroded, because the acid is very concentrated. A column with castiron plates may, therefore, be used.

Plates of sheet metal lined with lead, or Volvic lava with leaden or porcelain caps, may .also be utilized.

The process, whereby benzene may be sulphonated in a continuous manner, supplies the whole of the advantages which continuity offers in every industrial operation; more particularly, the same will secure a thorough homogeneity in the product obtained, a result which cannot be attained by the discontinuous operations. 7

Moreover, with the said process, the employment of mechanical agitations will be unnecessary, in fact, the necessary stirring will be produced in a perfect way by the intimate bubbling of the vapour through the sulphuric aci What I claim is: Y

1. A process of sulfonating benzene in a continuous manner, which comprises converting the benzene, into a vaporized condition and bringing such vapor into continuous, intimate .and methodical contact with heated concentrated sulfuric acid, supplying the heated sulfuric acid in-a' continuous manner, and removing the benzene sulfonic acid continuously.

2. A process of continuously sulfonating impure benzene mixed with oils which comprises converting the impure benzene into a vapor, bringing the vapor continuously into intimate contact with a continuous counter current of heated sulfuric acid, continuously removing the benzene sulfonic acid prodnot, and separately therefrom continuously removing unsulfonated oils.

3. A pgocess of continuously sulfonating impure nzene contained in admixture with unsulfonatable oils, which process comprises converting the impure benzene into a vapor, continuously bringing the said vapor into prolonged intimate contact with a continuous flowing hot current of concentrated sulfuric acid, continuously removing the "a descending. current of concentrate mas er liquid product containing the benzene sul- 5. A continuous process of making a sulfonic acid compound of an aromatic hydrocarbon, which comprises causing an upwardlyfiowing current of vapors containing said aromatic hydrocarbon to meet and be brought" into intimate and methodical contact with a downwardly flowing current of hot concentrated sulfuric acid and continuously drawing off the excess of sulfuric acid and-the sulfonic acid compound produced. 4

6. A continuous process for the manufacture of a sulfonic acid of an aromatic hydrocarbon by causing the vaporof the hydrocarbon to come into contact with a descending current of sulfuric acid heated to a temperature above that at which the hydrocarbon boils, and continuously removing in the vapor phase any unsulfonated vaporizable material present, and also continuously removing in the li uid phase any excess of sulfuric acid and t e aromatic sulfonic acid.

7. A continuous process for the manufacture of a sulfonic acid of benzene by causing the vapor of benzene to come into contact with 'a descending current of sulfuric acid, and continuously removing in the vapor phase any unsulfonated vaporizable ma-.

terial present, and also continuously removing in the liquid phase any excess of sulfuric acid and the benzene sulfonic acid.

8. A' continuous process for the manufac ture of sulfonic acid of benzene by causing the vapor of benzene to come into contact with a descending current of sulfuric acid, heated and maintained at a temperature not below that at which benzene boils, and continuously removing in the vapor phase any unsulfonated vaporizable material present, and also continuously removing in the liquid phase any excess of sulfuric acid and the benzene sulfonic acid.

'9. A continuous process for the manufacture of a sulfonic acid of benzene by causing the vapor o'fbenzene to rise throu h a tower in which stream of sulfuric acid is descending over obstructions to break and izable' material present, and also continuously removing in the liquid phase an excess of sulfuric acid and the benzene sul onic acid.

19. A continuous process for the manufacture of a sulfonic acid of benzene by causing the vapor of benzene to rise through a tower in which a stream of sulfuric acid, heated and maintained at a temperature not below that at which benzene boils is descending over obstructions to break and retard its fall. and continuously removing in the vapor phase any unsulfonated vaporizable material present, and also continuously removing in the liquid phase any excess of sulfuric acid and the benzene sulfonic acid.

11. A continuous process for the manufacture of sulfonic acids of benzene by causing the vapors of benzene to come into contact with a descending current of sulfuric acid, and continuously removing in the vapor phase the unacted on benzene and the water formed, and also continuously removing in the liquid phase the excess of sulfuric acid and the benzene sulfonic acids.

12. A continuous process for the manufacture of sulfonic acids of benzene by causing the vapors of benzene to come into contact with a descending current of sulfuric acid, heated and maintained at a temperature above that at which benzene boils, and continuously removing in the vapor phase the unacted on benzene and the water formed, and also continuously removing in the liquid phase the excess of sulfuric acid and the benzene sulfonic acids.

13. A continuous process for the manufacture of sulfonic acids of benzene by causing the vapors of benzene to rise through a tower in which a stream of sulfuric acid, heated and maintained at the temperature at which benzene boils, is descending over obstructions to break and retard its fall, and continuously removing in the vapor phase the unacted on benzene and the water formed, and also continuously removing in the liquid phase the excess of sulfuric acid and the benzene sulfonic acids.

14:. A continuous process for the manufacture of sulfonic acids of aromatic hydrocarbons by causing the vapors of the hydrocarbon to mix with the vapors of sulfuric acid, and continuously removing in the vapor phase the unacted on aromatic hydrocarbonsand the water formed, and also continuously removing in the liquid phase the excess of sulfuric acid and the aromatic sulfonic acids.

15. A continuous process for the manufacture ofsulfonic acids of aromatic hydrocarbons by causing the vapors of the hydrocarbon to come into contact with a descendmg current of sulfuric acid, and continuously removing in the vapor phase the unacted on aromatic hydrocarbons and the water formed, and also continuously removing in the liquid phase the excess of sulfuric acid and the aromatic sulfonic acid. b

16. A continuous process for the manufacture of sulfonic acids of aromatic hydrocarbons by causing the vapors of the hydrocarbon to come into contact with a descending current of sulfuric acid heated to the temperature at which the hydrocarbon boils and continuously removing in the vapor phase the unacted on aromatic hydrocarbons and the water formed, and also continuously removing in the liquid phase the excess of sulfuric acid and the aromatic sulfonic acids.

17; A continuous process for the manufacture of sulfonic acids of aromatic hydrocarbons by causing the vapors of the hydrocarbons to rise through a tower in which a stream of sulfuric acid heated to the temperature at which the hydrocarbon boils is descending over obstructions to break and retard its fall, and continuously removing in the vapor phase the unacted on aromatic hydrocarbons and thewater formed, and also continuously removing in the liquid phase the excess of sulfonic acid and the.

aromatic sulfonic acids.

18. A continuous processv for the manufacture of sulfonic acids of aromatic hydrocarbons by causing the vapors of the hydrocarbonto rise through a tower in which a stream of sulfuric acid heated to a temperature above that at which the hydrocarbon boils is descending over obstructions to break and retard its fall, and continuously removing in the vapor phase the unacted on aromatic hydrocarbons and the water formed, and also continuously removing in the liquid phase the excess of sulfuric acid and the aromatic sulfonic acids.

In testimony whereof I have signed my name to this specification.

PIERRE ALEXANDRE BARBET.

Witnesses:

LUCIEN PAILLABER, CHAS. P. PREssLY. 

